EP1896482A2 - Enzym-katalysiertes verfahren zur herstellung makrozyklischer polyester-oligomere - Google Patents

Enzym-katalysiertes verfahren zur herstellung makrozyklischer polyester-oligomere

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Publication number
EP1896482A2
EP1896482A2 EP06772489A EP06772489A EP1896482A2 EP 1896482 A2 EP1896482 A2 EP 1896482A2 EP 06772489 A EP06772489 A EP 06772489A EP 06772489 A EP06772489 A EP 06772489A EP 1896482 A2 EP1896482 A2 EP 1896482A2
Authority
EP
European Patent Office
Prior art keywords
solvent
enzyme
dicarboxylic acid
component
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06772489A
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English (en)
French (fr)
Inventor
Robert Dicosimo
Scott C. Jackson
Ana Panova
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1896482A2 publication Critical patent/EP1896482A2/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/81—Preparation processes using solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
    • C12P17/02—Oxygen as only ring hetero atoms
    • C12P17/08—Oxygen as only ring hetero atoms containing a hetero ring of at least seven ring members, e.g. zearalenone, macrolide aglycons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/34—Oligomeric, e.g. cyclic oligomeric

Definitions

  • the present invention relates to a process for the enzyme-catalyzed preparation of cyclic ester oligomers from dicarboxylic acids and/or dicarboxylic acid derivatives and diols, hydroxycarboxylic acids and/or hydroxycarboxylic acid esters, and/or linear ester oligomers using a reaction solvent mixture comprising a tertiary alcohol and non-alcoholic solvent.
  • Cyclic ester oligomers have been known for a long time; see for instance U.S. Patent 2,020,298. They are known to be present in varying, usually small, quantities in many linear polyesters and have been isolated from such linear polyesters; see for example A.G. Harrison, "Analysis of cyclic oligomers of poly(ethylene terephthalate) by liquid chromatography/mass spectrometry", Polymer, 38(10.), 2549-2555 (1997) and G. Wick, H. Zeitler, "Cyclic Oligomers in polyesters from diols and aromatic dicarboxylic acids", Angewandte Makromolekulare Chemie, (1983), 112, 59-94.
  • Macrocyclic polyester oligomers also can be prepared via the condensation of a dicarboxylic acid chloride with at least one bis(hydroxyalkyl) ester such as bis(4-hydroxybutyl) terephthalate in the presence of a highly unhindered amine or a mixture thereof with at least one other tertiary amine such as triethylamine.
  • the condensation reaction is conducted in a substantially inert organic solvent such as methylene chloride, chlorobenzene, or a mixture thereof. See, for example, U.S. Patent 5,231 ,161 to Brunelle et al.
  • Another method for preparing macrocyclic polyester oligomers or macrocyclic co-oligoesters is the depolymerization of linear polyester polymers in the presence of an organotin or titanate compound.
  • linear polyesters are converted to macrocyclic polyester oligomers by heating a mixture of linear polyesters, an organic solvent, and a transesterification catalyst such as a tin or titanium compound.
  • the solvents used, such as o-xylene and o-dichlorobenzene are usually substantially free of oxygen and water and solvents must be kept scrupulously dry when titanates are used as catalysts. See, for example, U.S. Patent 5,407,984 to Brunelle et al. and U.S.
  • polyesters can be made from carboxylic diacids or their diesters and diols using enzymes that catalyze transesterification; see for instance X.Y. Wu 1 et al., Journal of Industrial Microbiology and Biotechnology, vol. 20, p. 328-332 (1998); E. M.
  • a second component comprising at least one enzyme capable of catalyzing transesterification of esters, esterification of carboxylic acids, and/or hydrolysis of esters; wherein the solvent comprises about 30 to about 70 weight percent of at least one tertiary alcohol and about 30 to about 70 weight percent of at least one non-alcoholic solvent, wherein the weight percentages are based on the total weight of the solvent.
  • dicarboxylic acid refers to an organic compound that has two carboxylic acid groups.
  • dicarboxylic acid derivative refers to compounds derived from dicarboxylic acids such as a monoester, diester, or mixtures of two or more diesters, two or more monoesters, or at least one diester and at least one monoester.
  • the dicarboxylic acid or dicarboxylic acid derivative may be substituted with one or more functional groups such as alkyl, halogen, ether, thioether, and oxo (keto) that do not substantially interfere with the various reactions described in the processes herein.
  • the dicarboxylic acid or dicarboxylic acid derivative may include an aromatic ring as part of its structure.
  • the dicarboxylic acid or dicarboxylic acid derivative may be an aliphatic dicarboxylic acid.
  • hydroxycarboxylic acid ester means an organic compound that has a hydroxy group and a carboxylic acid ester group.
  • diol an organic compound having 2 hydroxyl groups or a simple derivative thereof.
  • the diol may be substituted with one or more functional groups such as halogen, ether, thioether, and oxo (keto) which do not substantially interfere with the various reactions described in the processes herein.
  • the diol may include an aromatic ring as part of its structure.
  • cyclic ester oligomer is meant a cyclic compound that is derived from at least one dicarboxylic acid and/or dicarboxylic acid derivative and at least one diol, at least one hydroxycarboxylic acid and/or hydroxycarboxylic acid ester, or a combination of at least one dicarboxylic acid and/or dicarboxylic acid derivative, at least one diol, and at least one hydroxycarboxylic acid and/or hydroxycarboxylic acid ester.
  • the moieties in the CEO derived from the diols, dicarboxylic acids and/or dicarboxylic acid derivatives, and hydroxycarboxylic acids and/or hydroxycarboxylic acid esters are connected by ester groups.
  • a “dimeric” CEO herein is meant a cyclic compound derived from at least one dicarboxylic acid and/or dicarboxylic acid derivative and at least one diol that has two units derived from dicarboxylic acid and/or dicarboxylic acid derivative and two units derived from diols, while if the dimeric CEO is made from a hydroxycarboxylic acid and/or hydroxycarboxylic acid ester it is derived from two such molecules.
  • Trimeric, tetrameric, etc. CEOs have analogous definitions.
  • CEOs may be made from two or more different dicarboxylic acids and/or dicarboxylic acid derivatives, two or more different diols, and/or two or more hydroxycarboxylic acids and/or hydroxycarboxylic acid esters.
  • CEOs will preferably have a degree of polymerization (DP) of about 1 to about 20, or preferably, about 1 to about 10, or more preferably, about 1 to about 5.
  • DP degree of polymerization
  • LEO linear ester oligomer
  • LEO linear ester oligomer
  • DP degree of polymerization
  • LEOs may be made by melt polymerization; solution polymerization; enzyme-catalyzed polymerization; the depolymerization of polyesters, including the thermal depolymerization of polyesters and the alcoholysis (e.g. methanolysis) and hydrolysis of polyesters; or other methods known to those skilled in the art.
  • melt polymerization see F.W. Billmeyer, Textbook of Polymer Science, 3 rd Edition (1984), John Wiley & Sons, pp. 25-48.
  • linear ester oligomer also encompasses mixtures containing both at least one linear compound derived from one or more dicarboxylic acids and/or dicarboxylic acid derivatives and one or more diols, one or more hydroxycarboxylic acids and/or hydroxycarboxylic acid esters, or a combination of one or more dicarboxylic acids and/or dicarboxylic acid derivatives, one or more diols, and one or more hydroxycarboxylic acids and/or hydroxycarboxylic acid esters and CEOs that are naturally present when LEOs are formed by either polymerization or depolymerization in the presence of a transesterification catalyst.
  • One type of preferred diol that may be used in the process of the present invention or from which LEOs used in the process of the invention are derived is an aliphatic diol, that is a diol in which each hydroxyl group is bound to different alkyl carbon atoms.
  • Other preferred diols include diols of the general formula HOCH 2 (CR 1 R 2 J n CH 2 OH, wherein R 1 and R 2 are each independently hydrogen or an alkyl group and n is an integer of 0 to 10, and preferably all R 1 and R 2 are hydrogen and especially preferably n is 0 or an integer of 1 to 4, and more preferably is n is 1 or 2.
  • Preferred diols include ethylene glycol, 1,3-propanediol, 1 ,4-butanediol, 1 ,5- pentanediol, 1 ,6-hexanediol, di(ethylene glycol), di(butylene glycol), di(propylene glycol), tri(butylene glycol), or mixtures thereof; dimethyl isophthalate with ethylene glycol, 1,3-propanediol, or 1 ,4-butanediol, 1 ,5- pentanediol, 1 ,6-hexanediol, di(ethylene glycol), di(butylene glycol), di(propylene glycol), tri(butylene glycol). Also preferred are alicyclic diols such as cyclohexane dimethanol. Aromatic diols such as hydroquinone may be used, as may thioethers.
  • Preferred dicarboxylic acids and/or dicarboxylic acid derivatives used in the process of the present invention or from which LEOs used in the invention are derived include aromatic dicarboxylic acids such as isophthalic acid, substituted isophthalic acids, terephthalic acid, substituted terephthalic acids, and 2,6-naphthalenedicarboxylic acid, and combinations thereof and their dicarboxylic acid derivatives. More preferred carboxylic acids are terephthalic acid and isophthalic acid and their dicarboxylic acid derivatives, and terephthalic acid and its dicarboxylic acid derivatives are especially preferred.
  • Preferred aliphatic dicarboxylic acids and/or dicarboxylic acid derivatives are adipic acid, glutaric acid, succinic acid, sebacic acid, and maleic acid and their dicarboxylic acid derivatives. It is particularly preferred that a dicarboxylic acid derivative in the form of a diester be used. Any combination of preferred dicarboxylic acid and/or dicarboxylic acid derivatives and the diols specified in the general formula above may be used in the present invention.
  • Preferred combinations of dicarboxylic acids and/or dicarboxylic acid derivatives and diols used in the process of the present invention or from which LEOs used in the invention are derived include dimethyl terephthalate with ethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, 1,5-pentanediol, 1 ,6- hexanediol, di(ethylene glycol), di(butylene glycol), di(propylene glycol), tri(butylene glycol), or mixtures thereof; dimethyl isophthalate with ethylene glycol, 1 ,3-propanediol, or 1 ,4-butanediol, 1 ,5-pentanediol, 1,6-hexanediol, di(ethylene glycol), di(butylene glycol), di ⁇ ropylene glycol), tri(butylene glycol), or mixtures thereof; dimethyl terephthal
  • hydroxycarboxylic acids and hydroxycarboxylic acid esters such as p-hydroxybenzoic acid and 2-hydroxyl-6-naphthoic acid and their esters will preferably be used as comonomers with diols and dicarboxylic acids and/or dicarboxylic acid derivatives.
  • reactants are dissolved in a solvent and reacted in the presence of at least one enzyme to form cyclic ester oligomers.
  • the reactants according to the present invention are one or more selected from the group consisting of at least one dicarboxylic acid and/or dicarboxylic acid derivative and at least one diol; at least one hydroxycarboxylic acid and / or at least one hydroxycarboxylic acid ester; and at least one linear ester oligomer.
  • the solvent used in the process of the present invention comprises about 30 to about 70 weight percent of at least one tertiary alcohol and about 30 to about 70 weight percent of at least on non-alcoholic solvent, or preferably about 40 to about 60 weight percent of at least one tertiary alcohol and about 40 to about 60 weight percent of at least on non-alcoholic solvent, based on the total weight of the solvent.
  • the tertiary alcohol solvent preferably has about 4 to about 8 carbon atoms and a general formula of (R 1 )(R 2 )(R 3 )COH, where R 1 , R 2 , and R 3 , are preferably independently selected from methyl, ethyl, n-propyl, /-propyl, n- butyl, /so-butyl, sec-butyl, ferf-butyl, n-pentyl, 2-pentyl, 3-pentyl, and other pentyl isomers.
  • Preferred tertiary alcohols are terf-amyl alcohol, 2,3-dimethyl- 2-butanol, and 3-ethyl-3-pentanol.
  • the non-alcoholic solvent is any solvent that does not contain a hydroxy group and that is miscible with the tertiary alcohol and that will dissolve the reactants.
  • Aromatic and/or chlorinated solvents are particularly suitable.
  • Preferred non-alcoholic solvents include toluene, benzene, xylene, chlorobenzene, dichlorobenzene, methylene chloride, methyl te/f-butyl ether, ethyl terf-butyl ether, methyl isobutyl ketone, and chloroform.
  • the enzyme used in the present invention is at least one enzyme that can catalyze the esterification of carboxylic acids, the transesterification of esters, and/or the hydrolysis of esters.
  • Typical types of enzymes that may be used include lipases, proteases, and esterases.
  • lipases for example, see the chapter RJ. Kazlaukas, et al., "Biotransformation with Upases," in
  • the enzyme is not soluble in the reaction mixture and may be attached to a solid material (supported or immobilized); see for instance G.E. Bickerstaff, Ed., Immobilization of Enzymes and Cells, Humana Press, Totowa, NJ, 1997.
  • Supports may include materials such as diatomaceous earth, polysaccharides (e.g., chitosan, alginate or carrageenan), titania, silica, alumina, polyacrylates and polymethacrylates, and ion exchange resins, and the enzyme may be adsorbed, covalently attached, or ionically attached, or in the form of crosslinked enzyme crystals (CLECS).
  • the enzyme may also be used without prior immobilization on a support and may be suspended in the stirred reaction mixture.
  • the specific activity of the immobilized enzyme is preferably about 0.1 IU/g immobilized enzyme to about 2000 IU/g immobilized enzyme, more preferably about 10 IU/g immobilized enzyme to about 500 IU/g of immobilized enzyme.
  • Preferred enzymes for use in the present invention are bacterial and fungal enzyme catalysts that are derived from organisms of the genera Aspergillus, Arthrobacter, Alcaligenes, Bacillus, Brevibacterium, Pseudomonas, Chromobacterium, Candida, Fusarium, Geotrichum, Humicola, Mucor, Pichia, Penicillium, Rhizomucor, Rhizopus or Thermus.
  • More preferred bacterial and fungal enzyme catalysts are derived from the genera and species Arthrobacter sp., Alcaligenes sp., Aspergillus niger, Aspergillus oryzae, Bacillus cereus, Bacillus licheniformis, Bacillus subtilis, Bacillus coagulans, Brevibacterium ammoniagenes, Burkholderia plantarii, Candida antartica, Candida cylindracea, Candidia lipolytica, Candida utilis, Candida rugosa, Chromobacterium viscosum, Fusarium solani, Geotrichum candidum, Humicola lanuginosa, Mucor sp., Mucor japonicus, Mucor javanicum, Mucor miehei, Pichia miso, Rhizomucor miehei, Rhizopus sp., Rhizopus nigricans, Rhizopus oryzae, Rhizopus arrhizus, Rhizopus delemar, Rhizopus niveus, Penici
  • Pseudomonas fluorescens or Pseudomonas putida are derived from Burkholderia cepacia, Pseudomonas sp, or Candida antartica, such as Candida antartica lipase B "CALB" (see Anderson et al., Biocatalysis and Biotransformation, 16:181-204 (1998)).
  • suitable, commercially-available, catalysts derived from C are suitable, commercially-available, catalysts derived from C.
  • antartica include, but are not limited to, Novozym® 435 (Product # L4777, Sigma-Aldrich, MO) and CHIRAZYME L-2, c-f C2, lyo (ID# 2207257, BioCatalytics, Pasadena, CA).
  • Preferred lipases derived from Burkholderia cepacia are PS-C "Amano” I and PS-D “Amano” I, available from Amano Enzyme, USA (Lombard, IL).
  • Preferred lipases derived from Pse ⁇ domonas sp. are ICR-107, ICR-108, and ICR-113, available from BioCatalytics.
  • derived from is meant that the enzyme can be isolated from or otherwise obtained from the specified organism. The enzyme may be used as part of a whole cell or a permeablized cell and may be partially purified or wholly purified.
  • the process of the present invention is run at temperatures at which the enzymes are active as catalysts for the desired reactions.
  • the upper temperature limit is typically that at which the enzyme ceases to be an active catalyst. Often this is the temperature at which the enzyme is denatured in the reaction medium. This upper temperature will vary with the enzyme used and the process ingredients, especially the pre-selected solvent, used. Typically these temperatures may range from about 0 0 C to about 130 0 C (the latter using specialty enzymes for higher temperatures, such as enzymes isolated from thermophillic microorganisms). Higher temperatures (but below the temperature at which the enzyme ceases to be active) are usually preferred because reaction(s) are often faster and solubilities of the various process ingredients are usually higher at higher temperatures. In one embodiment of the invention, a preferred temperature range is between about 40 and about 100 0 C and a more preferred temperature ranges is between about 60 and 80 0 C.
  • Preferred concentrations of the reactants in the process are at least 1 to about 25 w/v percent, more preferred concentrations are about 3 to about 15 w/v percent, based on the total weight of the reactants and the volume of the reaction mixture in g and mL, respectively.
  • the upper limit for these concentrations may be dictated in part by the desire to retain the reactants in solution. These concentrations are at the temperature at which the reaction is run. The concentration may be allowed to vary during the reaction. Reactants can be added either continuously or at intervals throughout the reaction to maintain or alter the concentration.
  • the reactants comprise dicarboxylic acid and/or dicarboxylic acid derivative and diol
  • the preferred ratio of dicarboxylic acid and/or dicarboxylic acid derivative to diol is between about 0.7:1 and 1.3:1.
  • the process of the present invention may be a batch, semi-batch, or continuous process.
  • the enzyme may be attached to a solid support or used unsupported. It may be present as a fixed bed or may be suspended in the solvent.
  • toluene When toluene is used, about 100 to about 200 ppm of water may be required to maintain enzyme activity over the course of the reaction and when methyl isobutyl ketone is used, about 400-500 ppm of water may be required.
  • the water level present in the solvent can be determined using Karl-Fischer titration or other methods known to those skilled in the art.
  • the reaction mixture is preferably continuously purged during the process, preferably with an inert gas, to remove the byproducts of the transesterification/esterification process, such as any alcohols that are formed.
  • the purging process may also remove water, requiring that water levels be maintained by the addition of water throughout the process in order to maintain enzyme activity. If the purging process removes solvent, additional solvent may have to be added throughout the process as well.
  • the CEOs formed by the process of the present invention may be recovered by any technique known in the art. For example, if the CEO is a solid, it may be recovered from solution by cooling the solution and/or removing some or all of the solvent and/or adding an additional solvent in which the CEO is not soluble, and recovering the solid CEO, for example, by filtration.
  • the CEO may be recovered by crystallization, liquid-liquid extraction, or the like.
  • Other techniques that could be used to isolate the CEOs from a mixture containing other components include selective crystallization; passing a solution containing the CEO's through a semi-permeable membrane; using a distillation technique such as short-path distillation; sublimation, melt-crystallization; the use of a selective solvent or selective adsorbant, or the like.
  • Preferred CEOs formed by the process of this invention are the dimer derived from 1 ,4-butanediol and dimethyl terephthalate (3,8,15,20- tetraoxatricyclo[20.2.2.210,13]octacosa-10,12,22,24,25,27-hexaene-
  • CBPT 2,9,14,21-tetrone
  • CBPT 2,9,14,21-tetrone
  • the trimer formed from 1 ,4-butanediol and dimethyl terephthalate (3,8,15,20,27,32- hexaoxatetracyclo[32.2.2.210, 13.222,25]dotetraconta- 10,12,22,24,34,36,37,39,41-nonaene-2,9,14,21 ,26,33-hexone
  • CEOs are higher oligomers derived from 1 ,4-butanediol and dimethyl terephthalate, 1 ,3-propanediol and dimethyl terephthalate, di(ethylene glycol) and dimethyl terephthalate; oligomers derived from 1 ,4- cyclohexanedimethanol and dimethyl terephthalate; oligomers derived from 1 ,5-pentanediol and dimethyl terephthalate; oligomers derived from 1 ,6- hexanediol and dimethyl terephthalate; oligomers derived from ethylene glycol and dimethyl 2,6-naphthalenedicarboxylate; and CEOs derived from two or more of the above.
  • the CEOs formed by the process of the present invention may be polymerized to higher molecular weight linear polyesters, which have many applications in injection molding, blow molding, extrusion molding, fibers, filaments, and films and are useful for making durable and disposable goods.
  • the polymerization may occur in the process of forming the article, using processes such as, but not limited to, injection and rotational molding, resin film infusion, resin transfer molding, filament winding, powder coating to create a prepreg or film, hot melt prepreg preparation, compression molding, roll wrapping, and pultrusion.
  • the polymerization preferably occurs at temperatures above the melting point of the CEOs.
  • the polymerization is preferably done in the presence of a polymerization catalyst such as organotin compounds, titanate esters, carbenes, alkali metal salicylates, stannous alkoxides, organotin compounds, and metal acetylacetonates.
  • a polymerization catalyst such as organotin compounds, titanate esters, carbenes, alkali metal salicylates, stannous alkoxides, organotin compounds, and metal acetylacetonates.
  • Additives such as reinforcing agents, mineral fillers, and other additives may be added to the CEO's before or during the polymerization to linear polyesters. The resulting polyesters will incorporate these additives.
  • suitable additives can include glass fibers, fumed silica, titanium dioxide, calcium carbonate, chopped fibers, fly ash, glass microspheres, micro-balloons, crushed stone, nanoclay, linear polymers, boron nitride, colorants, pigments, magnetic materials, antioxidants, UV stabilizers, heat stabilizers, plasticizers, flame retardants, lubricants, and mold release agents.
  • the articles formed from the CEOs can include automotive body panels and chassis components, bumper beams, aircraft wing skins, windmill blades, fluid storage tanks, tractor fenders, tennis rackets, golf shafts, windsurfing masts, toys, rods, tubes, bars, stock, bicycle forks, and machine housings, and like.
  • DMT dimethyl terephthalate
  • BDO 1,4-butanediol
  • min means minute(s)
  • g means gram(s);
  • mg means milligram(s);
  • mM means millimolar;
  • GC means gas chromatography.
  • Dimethyl terephthalate (CAS # 120-61-6), and 1 ,4-butanediol (CAS # 110-63-4) were obtained from Aldrich Chemical Company (Milwaukee, Wisconsin) and were used as received.
  • ferf-Amyl alcohol (CAS# 75-85-4) was obtained from Aldrich Chemical Company (Milwaukee, Wisconsin). It was kept over activated 4A molecular sieves before use and had a water content of about 380 ppm.
  • Toluene (CAS# 109-88-3) was obtained from EMD Chemicals (Gibbstown, New Jersey) and was kept as obtained over activated 4A molecular sieves and had a water content of 130 ppm.
  • the primary product of the reactions of Examples 1, 2, 5, and 6 and Comparative Examples 1-4, 7 and 12-15 was CPBT (Structure 1). Additional higher cyclic oligomers were also formed.
  • the primary product of the reactions of Example 3 and Comparative Examples 8 and 9 is the dimeric CEO of 1 ,6-hexanediol and dimethyl terephthalate. Additional higher CEO's are also formed.
  • the primary product of the reactions of Example 4 and Comparative Examples 10 and 11 is the dimeric CEO of 1,5-pentanediol and dimethyl terephthalate. Additional higher CEO's are also formed.
  • Samples are analyzed by LC using the following method.
  • the reaction solvent used in the reaction mixture is stripped off under vacuum at a temperature of 30 to 50 0 C.
  • Chloroform is added to about 1 to 3 times the original reaction volume before the solvent is removed. In some cases, the reaction solvent is not stripped off and the chloroform is added directly to the reaction mixture. Sufficient chloroform is added to dissolve the products and any remaining reactants. The amount of chloroform added depends on the original concentrations of reactants used.
  • the unsupported or supported enzyme floats to the top of the chloroform while oligomers and unreacted diol and diester readily dissolve. An aliquot is removed from the clear solution and filtered.
  • Cyclic oligomer peaks are identified by retention time. Samples of pure cyclic oligomer extracted from the corresponding high molecular weight polymer or isolated from previous reactions are used to determine the retention times of the expected cyclic oligomer peaks. The identity of the peaks is independently confirmed by HPLC-MS. Concentrations of cyclic oligomers are determined using the internal standard and a response factor for the pure isolated oligomers relative to the standard. Apparent yields are based on the HPLC area percent of the cyclic components relative to the total area of all the peaks (other than the solvent and standard) observed in the HPLC.
  • Example 1 and Comparative Examples 1 and 2 A series of batch reactions were run in 40 mL glass vials reacting 1 ,4- butandiol (BDO) and dimethyl terephthalate (DMT) in the presence of the enzyme Novozym® 435.
  • the solvent used was a 50/50 by weight mixture of terf-amyl alcohol and toluene.
  • the solvent used was a 75/25 by weight mixture of terf-amyl alcohol and toluene.
  • Comparative Example 2 the solvent used was toluene.
  • the BDO and DMT each had a nominal concentration of about 70 mM in the solvent.
  • the nominal loading of the enzyme was 6 weight percent (which includes the enzyme support).
  • the reactions were run in glass vials placed in a single, temperature-controlled heating block. Agitation was provided by magnetic stirring bars. The reactions were run for 96 hours at 70 0 C. The head spaces of the vials were swept with nitrogen saturated with the corresponding solvent mixture at the reaction temperature to remove the byproduct methanol. At the end of the reaction, the solvent was stripped off under vacuum at moderate temperature (about 50 0 C), sufficient CHCI 3 to dissolve the reaction products and any unreacted starting material was added, and the mixture was agitated vigorously. The enzyme with support floated to the top. An aliquot of the resulting solution was taken for HPLC and GC analysis. HPLC analysis indicated >90% conversion based on the loss of DMT for all three reactions.
  • Example 1 the yield of cyclic oligomer was about 20%. In the case of Comparative Example 1 , the yield of cyclic oligomer was about 7%. In the case of Comparative Example 2, the yield of cyclic oligomer was about 9%.
  • Example 2 and Comparative Examples 3 and 4 A series of batch reactions were run in 40 ml_ glass vials reacting 1 ,4- butandiol (BDO) and dimethyl terephthalate (DMT) in the presence of the enzyme Novozym® 435.
  • BDO 1 ,4- butandiol
  • DMT dimethyl terephthalate
  • the solvent used was a 50/50 by weight mixture of te/f-amyl alcohol and toluene.
  • Comparative Example 3 the solvent used was a 75/25 by weight mixture of terf-amyl alcohol and toluene.
  • the solvent used was toluene.
  • the BDO and DMT each had a nominal concentration of about 75 mM.
  • the nominal loading of the enzyme was 6 weight percent (which includes the enzyme support).
  • the reactions were run in glass vials placed in a single, temperature-controlled heating block. Agitation was provided by magnetic stirring bars. The reactions were run for 168 hours at 70 0 C. The head spaces of the vials were swept with nitrogen saturated with the corresponding solvent mixture at the reaction temperature to remove the byproduct methanol. At the end of the reaction, the solvent was stripped off under vacuum at moderate temperature (about 50 0 C), sufficient CHCI 3 to dissolve the reaction products and any unreacted starting material was added, and the mixture was agitated vigorously. The enzyme with support floated to the top. An aliquot of the resulting solution was taken for HPLC and GC analysis. HPLC analysis indicated >90% conversion based on the loss of DMT for all three reactions.
  • Example 2 the yield of cyclic oligomer was about 25%. In the case of Comparative Example 3, the yield of cyclic oligomer was about 3%. In the case of Comparative Example 4, the yield of cyclic oligomer was about 5%. Comparative Examples 5-7
  • the batch reactions were done in 20 mL glass vials using a carefully controlled heated reaction block that was identical to that used in Examples 1 and 2 and Comparative Examples 1-4, as described above.
  • the solvent the solvent used was a 50/50 by weight mixture of ferf-amyl alcohol and toluene.
  • the solvent used was a 75/25 by weight mixture of ferf-amyl alcohol and toluene.
  • the solvent used was toluene.
  • the BDO and DMT each had a nominal concentration of about 70 mM in the solvent.
  • the nominal loading of the mesityl heterocyclic carbene was 0.24 weight percent.
  • a series of batch reactions between 1 ,6-hexanediol (HDO) and dimethyl terephthalate (DMT) is performed in 40-mL glass vials using a range of composition for reaction solvents, and using the enzyme Novozym® 435.
  • the solvent used is a 50/50 by weight mixture of te/ ⁇ -amyl alcohol and toluene.
  • the solvent used is a 75/25 by weight mixture of ferf-amyl alcohol and toluene.
  • the solvent used is toluene.
  • the HDO and DMT each has a nominal concentration of about 70 mM in the solvent.
  • the nominal loading of the immobilized enzyme is 6 weight percent.
  • the reactions are run in glass vials placed in a single, temperature-controlled heating block. Agitation is provided by magnetic stirring bars. The reactions are run for 96 h at 70 0 C. The head spaces of the vials are swept with nitrogen saturated with the corresponding solvent mixture at the reaction temperature to remove the by-product methanol. At the completion of the reaction, the solvent is stripped off under vacuum at moderate temperature (about 50 "C), sufficient CHCb to dissolve the reaction products and any unreacted starting material is added, and the mixture is agitated vigorously.
  • moderate temperature about 50 "C
  • the immobilized enzyme is separated from the mixture, and a sample of the resulting solution is analyzed by HPLC and GC.
  • HPLC analysis indicates >90 % conversion of DMT and HDO for all three reactions.
  • An improved yield of cyclic ester oligomers is observed in the case of Example 3 when compared to Comparative Examples 8 and 9.
  • Example 4 and Comparative Example 10 and 11 A series of batch reactions between 1 ,5-pentanediol (PDO) and dimethyl terephthalate (DMT) is performed in 40-mL glass vials using a range of composition for reaction solvents, and using the enzyme Novozym® 435.
  • the solvent used is a 50/50 by weight mixture of terf-amyl alcohol and toluene.
  • the solvent used is a 75/25 by weight mixture of te/ ⁇ -amyl alcohol and toluene.
  • the solvent used is toluene.
  • the PDO and DMT each has a nominal concentration of about 70 mM in the solvent.
  • the nominal loading of the immobilized enzyme is 6 weight percent.
  • the reactions are run in glass vials placed in a single, temperature-controlled heating block. Agitation is provided by magnetic stirring bars. The reactions are run for 96 h at 70 0 C. The head spaces of the vials are swept with nitrogen saturated with the corresponding solvent mixture at the reaction temperature to remove the by-product methanol. At the completion of the reaction, the solvent is stripped off under vacuum at moderate temperature (about 50 0 C), sufficient CHCI 3 to dissolve the reaction products and any unreacted starting material is added, and the mixture is agitated vigorously.
  • the immobilized enzyme is separated from the mixture, and a sample of the resulting solution is analyzed by HPLC and GC.
  • HPLC analysis indicates >90 % conversion of DMT and HDO for all three reactions.
  • An improved yield of cyclic ester oligomers is observed in the case of Example 4 when compared to Comparative Examples 10 and 11.
  • a series of batch reactions between 1,4-butanediol (BDO) and dimethyl terephthalate (DMT) is performed in 40-mL glass vials using a range of composition for reaction solvents, and using the enzyme Novozym® 435.
  • the solvent used is a 50/50 by weight mixture of 2,3- dimethyl-2-butanol and toluene.
  • the solvent used is a 75/25 by weight mixture of 2,3-dimethyl-2-butanol and toluene.
  • the solvent used is toluene.
  • the BDO and DMT each has have a nominal concentration of about 70 mM in the solvent.
  • the nominal loading of the immobilized enzyme is 6 weight percent.
  • the reactions are run in glass vials placed in a single, temperature-controlled heating block. Agitation is provided by magnetic stirring bars. The reactions are run for 96 h at 70 0 C. The head spaces of the vials are swept with nitrogen saturated with the corresponding solvent mixture at the reaction temperature to remove the by-product methanol. At the completion of the reaction, the solvent is stripped off under vacuum at moderate temperature (about 50 0 C), sufficient CHCI 3 to dissolve the reaction products and any unreacted starting material is added, and the mixture is agitated vigorously. The immobilized enzyme is separated from the mixture, and a sample of the resulting solution is analyzed by HPLC and GC. HPLC analysis indicates >90 % conversion of DMT and HDO for all three reactions. An improved yield of cyclic ester oligomers is observed in the case of Example 5 when compared to Comparative Examples 12 and 13.
  • a series of batch reactions between 1,4-butanediol (BDO) and dimethyl terephthalate (DMT) is performed in 40-mL glass vials using a range of composition for reaction solvents, and using the enzyme Novozym® 435.
  • the solvent used is a 50/50 by weight mixture of 3- ethyl-3-pentanol and toluene.
  • the solvent used is a 75/25 by weight mixture of 3-ethyl-3-pentanol and toluene.
  • the solvent used is toluene.
  • the BDO and DMT each has a nominal concentration of about 70 mM in the solvent.
  • the nominal loading of the immobilized enzyme is 6 weight percent.
  • the reactions were run in glass vials placed in a single, temperature-controlled heating block. Agitation is provided by magnetic stirring bars. The reactions are run for 96 h at 70 0 C. The head spaces of the vials are swept with nitrogen saturated with the corresponding solvent mixture at the reaction temperature to remove the by-product methanol. At the completion of the reaction, the solvent is stripped off under vacuum at moderate temperature (about 50 0 C), sufficient CHCI 3 to dissolve the reaction products and any unreacted starting material is added, and the mixture is agitated vigorously.
  • the immobilized enzyme is separated from the mixture, and a sample of the resulting solution is analyzed by HPLC and GC.
  • HPLC analysis indicates >90 % conversion of DMT and HDO for all three reactions.
  • An improved yield of cyclic ester oligomers is observed in the case of Example 6 when compared to Comparative Examples 14 and 15.
  • a 200 mg sample of each of the enzymes in Table 1 was added to its own 8 mL reaction vial equipped with a magnetic stirring bar.
  • DMT (97 mg), DEG (500 ⁇ l_ of a solution prepared by dissolving 530 mg of DEG in 5 mL of toluene), and 1.4 mL of toluene were added to each vial.
  • the resulting concentration of DEG was about 0.25 M.
  • the vials were incubated at 50 0 C with stirring for 96 hours under a flow of nitrogen saturated with toluene.
  • a series of batch reactions between 1 ,6-hexanediol (HDO) and dimethyl terephthalate (DMT) is performed in 40-mL glass vials, where each reaction uses specified reaction solvent and one of the following enzymes (see Table 1): PS-C "Amano" I, PS-D "Amano” I, ICR-107, ICR-108, ICR-113.
  • the solvent used is a 50/50 by weight mixture of te/f-amyl alcohol and toluene.
  • the solvent used is a 75/25 by weight mixture of terf-amyl alcohol and toluene.
  • the solvent used is toluene. A total of 15 reactions are run.
  • the HDO and DMT each has a nominal concentration of about 70 mM in the solvent.
  • the nominal loading of the immobilized enzyme is 6 weight percent.
  • the reactions are run in glass vials placed in a single, temperature-controlled heating block. Agitation is provided by magnetic stirring bars. The reactions are run for 96 h at 70 0 C. The head spaces of the vials are swept with nitrogen saturated with the corresponding solvent mixture at the reaction temperature to remove the by-product methanol. At the completion of the reaction, the solvent is stripped off under vacuum at moderate temperature (about 50 0 C), sufficient CHCI 3 to dissolve the reaction products and any unreacted starting material is added, and the mixture is agitated vigorously.
  • the immobilized enzyme is separated from the mixture, and a sample of the resulting solution is analyzed by HPLC and GC.
  • HPLC analysis indicates at least about 10 % conversion of DMT and HDO for each of the reactions.
  • An improved yield of cyclic ester oligomers is observed in the case of Example 7 when compared to Comparative Examples 17 and 18.
  • a series of batch reactions between 1,5-pentanediol (PDO) and dimethyl terephthalate (DMT) is performed in 40-mL glass vials where each reaction uses specified reaction solvent and one of the following enzymes (see Table 1): PS-C "Amano" I, PS-D "Amano” I, ICR-107, ICR-108, ICR-113.
  • the solvent used is a 50/50 by weight mixture of ferf-amyl alcohol and toluene.
  • the solvent used is a 75/25 by weight mixture of fert-amyl alcohol and toluene.
  • the solvent used is toluene.
  • a total of 15 reactions are run.
  • the PDO and DMT each has a nominal concentration of about 70 mM in the solvent.
  • the nominal loading of the immobilized enzyme is 6 weight percent.
  • the reactions are run in glass vials placed in a single, temperature-controlled heating block. Agitation is provided by magnetic stirring bars. The reactions are run for 96 h at 70 0 C. The head spaces of the vials are swept with nitrogen saturated with the corresponding solvent mixture at the reaction temperature to remove the by-product methanol.
  • the solvent is stripped off under vacuum at moderate temperature (about 50 °C), sufficient CHCI 3 to dissolve the reaction products and any unreacted starting material is added, and the mixture is agitated vigorously.
  • the immobilized enzyme is separated from the mixture, and a sample of the resulting solution is analyzed by HPLC and GC.
  • HPLC analysis indicates at least about 10 % conversion of DMT and HDO for each of the reactions.
  • An improved yield of cyclic ester oligomers is observed in the case of Example 8 when compared to Comparative Examples 19 and 20.
  • a series of batch reactions between 1,4-butanediol (BDO) and dimethyl terephthalate (DMT) is performed in 40-mL glass vials where each reaction uses specified reaction solvent and one of the following enzymes (see Table 1): PS-C "Amano" I 1 PS-D "Amano" I, ICR-107, ICR-108, ICR-113.
  • the solvent used is a 50/50 by weight mixture of 2,3- dimethyl-2-butanol and toluene.
  • the solvent used is a 75/25 by weight mixture of 2,3-dimethyl-2-butanol and toluene.
  • the solvent used is toluene. A total of 15 reactions are run.
  • the BDO and DMT each has have a nominal concentration of about 70 mM in the solvent.
  • the nominal loading of the immobilized enzyme is 6 weight percent.
  • the reactions are run in glass vials placed in a single, temperature-controlled heating block. Agitation is provided by magnetic stirring bars. The reactions are run for 96 h at 70 0 C. The head spaces of the vials are swept with nitrogen saturated with the corresponding solvent mixture at the reaction temperature to remove the by-product methanol. At the completion of the reaction, the solvent is stripped off under vacuum at moderate temperature (about 50 0 C), sufficient CHCI 3 to dissolve the reaction products and any unreacted starting material is added, and the mixture is agitated vigorously.
  • the immobilized enzyme is separated from the mixture, and a sample of the resulting solution is analyzed by HPLC and GC.
  • HPLC analysis indicates at least about 10 % conversion of DMT and HDO for each of the reactions.
  • An improved yield of cyclic ester oligomers is observed in the case of Example 9 when compared to Comparative Examples 21 and 22.
  • a series of batch reactions between 1,4-butanediol (BDO) and dimethyl terephthalate (DMT) is performed in 40-mL glass vials where each reaction uses specified reaction solvent and one of the following enzymes (see Table 1): PS-C "Amano" I, PS-D "Amano” I 1 ICR-107, ICR-108, ICR-113.
  • the solvent used is a 50/50 by weight mixture of 3-ethyl- 3-pentanol and toluene.
  • the solvent used is a 75/25 by weight mixture of 3-ethyl-3-pentanol and toluene.
  • the solvent used is toluene. A total of 15 reactions are run.
  • the BDO and DMT each has a nominal concentration of about 70 mM in the solvent.
  • the nominal loading of the immobilized enzyme is 6 weight percent.
  • the reactions were run in glass vials placed in a single, temperature-controlled heating block. Agitation is provided by magnetic stirring bars. The reactions are run for 96 h at 70 0 C. The head spaces of the vials are swept with nitrogen saturated with the corresponding solvent mixture at the reaction temperature to remove the by-product methanol. At the completion of the reaction, the solvent is stripped off under vacuum at moderate temperature (about 50 0 C), sufficient CHCI3 to dissolve the reaction products and any unreacted starting material is added, and the mixture is agitated vigorously.
  • the immobilized enzyme is separated from the mixture, and a sample of the resulting solution is analyzed by HPLC and GC.
  • HPLC analysis indicates at least about 10 % conversion of DMT and HDO for each of the reactions.
  • An improved yield of cyclic ester oligomers is observed in the case of Example 10 when compared to Comparative Examples 23 and 24.

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EP06772489A 2005-06-07 2006-06-07 Enzym-katalysiertes verfahren zur herstellung makrozyklischer polyester-oligomere Withdrawn EP1896482A2 (de)

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DE3224707A1 (de) 1982-07-02 1984-01-05 Chemische Werke Hüls AG, 4370 Marl Verfahren zur herstellung von makrocyclischen ketolactonen
US5466744A (en) * 1990-11-05 1995-11-14 General Electric Company Polymerization of macrocyclic poly(alkylene dicarboxylate) oligomers
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US5407984A (en) * 1994-08-31 1995-04-18 General Electric Company Process for preparing macrocyclic polyester oligomers
US5668186A (en) 1996-03-20 1997-09-16 General Electric Company Process for depolymerizing polyesters
US5661214A (en) * 1996-08-05 1997-08-26 General Electric Company Titanate esters useful as polymerization initiators for macrocylic polyester oligomers
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